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NITED STATES PATENT ()FFICEa JOHN H. STEVENS, OF NEWARK, NEW JERSEY, ASSIGNOR, BY MESNE ASSIGNMENTS, TO THE CELLULOID COMPANY, OF SAME PLACE.

MANUFACTURE OF SOLID OR MASSIVE COMPOUNDS OF PYROXYLINE.

SPECIFICATION forming part of Letters Patent No. 543,108, dated July 23 1895.

Application filedJune 9,1890, Serial No. 354,735. (No specimens.)

To all whom, it may concern.-

' Be it known that I, JOHN H. STEVENS, of the city of Newark, county of Essex, and State of New Jersey, have invented certain new and useful Improvements in the Manufacture of Solid or Massive Compounds of Pyroxyline, of whichimprovement the followingis a specification.

This invention relates to the manufacture,

' pounds to which this invention relates is the one employed in the arts as an imitation of various natural substances. It is distinguished from the solid explosive compounds not only by the difference in solubility of the pyroxyline employed, but by the widely-different characteristics and uses of the present compound and the explosive compositions, one being valuable by reason of its stable na- -ture, plasticity, solidity, color effects, and

susceptibility,and to artistic and mechanical manipulations, while the other generally possesses none of these qualities, but its special valueis due to its loosely-held components, which are brought together and associated for the express purpose of forming a compound instantaneously resolvable into gases, the valuable properties of explosives being only exhibited at the moment of disorganization.

The state of the art and the properties and uses of the pyroxyline compounds to which this invention relates are set forth in the United States Letters Patent granted to me on April 10, 1894, No. 517,987, which was granted to me on application therefor filed simultaneously with the application for the present patent.

The distinctive novelty of this present improvement in the artor manufacture consists My invention is based upon the fact that dinitro-toluol, when melted by heat, is an active solvent of soluble pyroxyline, and that it is especiallyapplicable, not only as a solvent. when heated, but also by reason of the peculiar properties of its combination with pyroxylinein this particular class of compounds, the discovery of which facts I believe to be entirely original with me.

The'diftlculties connected with the discovery and application of pyroxyline solvents suitable for practical use are mentioned in Patent No. 517,987, before referred to.

In combining dinitro-toluol with pyroxyline I form a compound possessing many of the advantages over the well-known camphorpyroxyline compounds which I have secured in the acetanilid-pyroxyline compound, and as described in my Patent No. 517,987, already referred to.

The dinitro-toluol differs from the phenylacetamide (acetanilid) by possessing more odor and color and the power of forming a pyroxyline compound which is more plastic under heat or more easily manipulated at elevated temperatures than the phenylacetamide (acetanilid) combinations. Otherwisethedescription of the phenylacetamide (acetanilid) and its'compounds with pyroxyline in Patent No. 517,987 willapply to the dinitro-toluol and its pyroxyline compounds.

In making the combinations with dinitrotoluol I also prefer the processes described in Patent No. 517,987. This present invention can also be used with excellent results in connection with the phenylacetamide (acetanilid) lid) as the solid solvent. The proportions between the two substances can be varied at will, and compounds of different degrees of susceptibility to heat, when molded or manipulated, can be thus produced. An excess of the dinitro-toluol gives more plasticity than an excess of the phenylacotamide (acetanilid), and the proportion of the mixed solvent can be about the same as that recommended for either the dinitro-toluol or the phenylacetamide (acetanilid) alone.

In using camphor it has been customary to use mainly ethylic or methylic alcohols, although to a less extent otherliquids have been used. I have found that dinitro-toluol is quite distinct from camphor in its solubility, and the use of ethylic and methylic alcohols in connection with it is not as practicable as when they are employed with camphor. This arises from the fact that dinitro-toluol is almost insoluble in grain alcohol, (ethylic alco hol). Even one hundred parts of such alcohol does not seem to dissolve it. It is more soluble in methylic alcohol, (wood spirits,) about ten parts of such alcohol appearing todissolve one part of the dinitro-toluol. I prefer and recommend acetone as the liquid agent in'my present compound because it has been found to be a superior menstruum for the dinitro-toluol. After various experiments I have ascertained that dinitro-toluol is readily soluble in a small portion or about one and one-half parts of acetone. All of these solubiiities just given are at the ordinary temperature of the atmosphere. This solvent power of the acetone enables me to use it with great success in making pyroxyline compounds where a liquid solvent is required to be employed, and I obtain a result impossible with either ethylic or methylic alcohols. I have made this employment of acetone the subject of another application, to be filed simultaneously herewith, Serial No. 354,787, and designated as Case D. I would say, however, that both the ethylic and the methylic alcohols mentioned can be employed in connection with dinitro-toluol in these solid compounds, and they may be rendered quite efficient by simply heating the receptacle containing the mixture of pyroxyline, dinitrotoluol, and either of the alcohols just mentioned to a sufficiently high temperature to cause it to cohere or to bring it to a doughlike state. This heating of the compound in a closed receptacle is similar in the reasons therefor and the effect of the heating to the operation recommended in my Patent No. 269,342, of December 19, 1882, where I refer to the mixture of pyroxyline, dinitro-benzene, and alcohol. After this treatment the combination will be in a condition suitable for mastication in heated rolls. These precautions are unnecessary when acetone is employed, for the reason above given.

I refer to the descriptions in Patent No. 517,987 as to the solvent action of the phenylacetamide (acetanilid) on the pyroxyline when it is heated in connection therewith, even in the presence of a small proportion of liquid solvent, insufficientin itself to cause the compound to flow or change its shape; also, to the solvent action of the phenylacetamide (acetanilid) under heat when the combination of solid solvent and pyroxyline is in a converted or homogeneous condition, regardless of the process which brought it to that state. I make the same claim with regard to the solvent action of the dinitro-toluol, as I mean to be distinctly understood as claiming that, even in the presence of the small proportion of liquid solvent, the dinitrotoluol would be acting asapyroxyline solvent when subjected to heat and pressure.

My dinitro-toluol-pyroxyline compounds, whether made by simply combining dinitrotoluol and pyroxyline, or formed with the aid of liquid solvents in heated rolls, or by dissolving the pyroxyline in a liquid solution of dinitro-toluol, or in any equivalent manner, when in a dry or seasoned condition ora comparatively hard state, due to the absence or removal of sufficient liquid to soften it, is in such a condition that when it is subjected to heat and pressure it depends for its plastic property or susceptibility of being [lowed under heat and pressure upon the solvent powers of the dinitro-toluol, and therefore any such heating or the production of these conditions or efiects is an employment of the dinitro-toluol, made etiicient by heat, as a solvent of pyroxyline. As to proportions, the dinitro-toluol can be used in smaller proportions than the phenylacetamide (acetanilid) of Patent No. 517,987. This is on account of its superior plastic effects. I would recommend, however, about the same proportions and limitations as are described for the phenylacetamide (acetauilid) in Patent No. 517,987.

In making a compound without the use of liquid solvents good proportions are: one hundred parts by weight of pyroxyline and fifty parts of dinitro-toluol and quantum suffict't ofany pigment or coloring matter, as desired.

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If the ingredients of the above mixture have been intimately combined with sufficient care, and thoroughlyfreed from adherent moisture they can be converted intoasolid homogene ous mass by subjecting the mixture to pressure (say of one thousand pounds to the square inch) and heated to about the melting-point of the dinitro-toluol employed, (usually from to Fahrenheit.) The compound, however, under these conditions is so stiff, or fiows so slowly under heat, that it is best to operate on small masses at a time, and also to have the shape of the pressed pulp conform, as closely as possible, to the final shape desired in the solid converted product. The operation requires great care, for no one part of the mass must be overheated while waiting to have the heat penetrate the other parts, it being well known that a uniform temperature operator when applying heat to the mass be-,

fore conversion has been efiected. To facilitate the union ofthe different ingredients of the compound, it-is best to subject the wet pulp, from which the product is originally made, to enormous pressure while it is being dried. This, by compacting the ingredients, renders their conversion a simpler operation.

In obtaining a solid product without the aid of liquid solvent the operation must beperformed by one having a thorough knowledge of pyroxylineand itsaction under heat and pressure, and the aboveinstructions should be carefully observed.- In every case, also, the die or mold or other apparatus used should be arranged so that the compound is not entirely excluded from the atmosphere, so that in case a careless preparation of'the ingredients or careless manipulation by the operator shouldproduce a burning ofthe materials the released gases willfind a ready outlet and the decomposition of the material would be discovered in time. This can be done by having the parts of the apparatus fit loosely. For

instance, where a die is used the plunger can have a, space of, say, one-eighth of an inch. around it. These precautions are not necessary with a carefully-prepared material after it has been converted into a solid compound suitable for subsequent remolding, as above described, for the thoroughly-converted product made by this process simply resembles what is ordinarily recognized as a well-seasoned compound of pyroxyline, and can be treated as such. Where, however, the dinitrotoluol is employed in conjunction with liquid solvents, Irecommend the following method of manufacture: The dried cake produced by pressing the wet pulp containing the dinitrotoluol and coloring materials between blottingpapers is to be broken in small pieces, and if it is desired to use a comparatively small proportion of liquidsolvent, simple or compound, such liquidis then mixed in proportion of from forty parts to fifty parts to eachone hundred parts pyroxyline present. For this purpose I prefer to use acetone as the liquid, as already explained. This mixture is allowed to stand in an air-tight vessel for several hours in order to allow the acetone to become fairly well diffused throughout the mass. After this is done the mixture is ready for mastication, which is performed in heated rollers at a temperature. of 120 Fahrenheit, as is customary in manufacturing such pyroxyline compounds as this patent relates to. Afterthis operation is proceeded with far enough, as is well understood, the material is removed from the rollers and receives subsequent treatment in so-called stuffing machinery or presses in order to solidify it and form it into various shapes-such as tubes, rods, and blocks-from which sheets can be cut, as is understood and more particularly described in my Patent- No. 517,987. 7

Among the advantages I claim for this new compound of pyroxyline, of which dinitrotoluol isthesolvent, are that the operations of mixing are carried on without the loss by evaporation incident to the use of camphor, thus permitting a freer use of drying methods and relieving the work-room from the camphor fumes. There is practically. no loss of the solid solvent by evaporation, and the liquids can be'entirely removed from the compound without impairing its plasticity whenheated at fairly-low temperatures. Many difficulties, more or less connected with or due to the continual warping of the older materials containing camphor, will be remedied ,by the application of my new compound to such cases. I would mention drawing instruments, parts of machinery, and articles requiring to be nicely fitted togetherlil e boxes, for example. My new compound will also be found much harder and more plastic, than compounds made with camphor. When used alone as a solvent, of course it is "limited to what is known as the f solid or plastic process of conversion; but this process may also be practiced, as above shown, by adding such small quantities of liquid solvents as will not make the compound flow or result in what is known as the fluid process of conversion. I have filed. a separate simultaneous application, Serial No. 354,787, and designated as Case D, for the use of this ingredient in. the fluid process of conversion, because special means are often required to render it effective, in the fluid compounds and to prevent it from injuring them by its presence, means of remedying which I have specified and claimed in several other applications, and the use of the ingredient in thesolid or plastic process is therefore to be definitely distinguished. As the result of numerous experiments I have demonstrated'its extraordinary utility in the solid varieties, as herein described, and the novelty of my present invention depends on such demonstration, according to the principles hereinbefore set forth or referred to.

I wish it'distinctly understood that even if pyroxyline is treated by the liquid mode .of conversion and the liquid is then evaporated and then dinitro-toluol be present in proportionssuch as to produce, after evaporation of the liquid solvents, what is substantially a compound of pyroxyline and dinitrotoluol, any heating or treatment of the resulting solid which will develop the latent solvent power of the dinitro-toluol, so that it will soften, dissolve, or make plastic the pyroxyline, is a use of the solventpowers of the dinitro-toluol, as already explained, and such operation is within the invention herein set forth.

The use of diuitro-toluol in solventor massive compounds of pyroxyline is not incompatible with the employment of camphor. On the contrary, the use of dinitro-toluol in the camphor compounds imparts some of its properties to such compounds-namely, by enabling the camphor to melt at a much lower temperature by reason of its association there with, and thus removing one of the objectionable features connected with the employment of camphor alone as a solid solvent. Consequently compounds containing this combined solvent can be more readily molded at safe temperatures without the necessary presence of a residue of the alcoholic or other liquid solvent, thus rendering the manipulation of the camphor compound more uniform and certain. In making such compound I grind together the camphor dinitro-toluol, pyroxyline, and other necessary ingredients, preferably in the presence of water and then dried in the regular manner. Ethylic and methylic alcohols or other suitable liquid may then be added to the mixture and the whole stirred together and left over night in an air-tight vessel. The resultant mass is masticated in rolls and formed into shapes in the usual well-known manner. Good proportions for this latter compound are, one hundred parts pyroxyline, forty parts camphor, ten parts dinitro-toluol, and about forty to forty-five parts of either of the alcohols mentioned, or acetone can be used in place of the alcohol. The respective proportions of camphor and dinitro-toluol can be varied at will. This camphor dinitro-toluolpyroxyline compound has been separated from the present specification, and is made the subject of a separate application, Serial No. 494,298, where it will be found more particularly described.

What I claim, and desire to secure by Letters Patent, is-

1. The process of manufacturing pyroxyline compounds which consists in intimately mixing pyroxyline and di-nitro-toluol and sulrjecting such mixture to heat and pressure sullicientto render the compound plastic, substantially as described.

2. The process of manufacturing solid or massive pyroxyline compounds, which (3011' sists in mixing pyroxyline, di-nitro-toluol and a liquid menstruum or liquid menstrua and subsequently subjecting the resulting compound to heat and pressure sufficient to'render the compound plastic,substantially as set forth.

3. The product resulting from the process of manufacturing the solid or massive pyroxyline compounds which consists in mixing pyroxyline and di -nitro-toluol and subsequently subjecting the resulting compound to heat and pressure sufficient to render the compound plastic, substantially as described.

4. The product resulting from the process of manufacturing solid or massive pyroxyline compounds, which consists in mixing pyroxyline, di-nitro-toluol and a liquid menstruum, or liquid menstrua, and subsequently subjecting the resulting compound to heat and pressure sufficient to render the compound plastic, substantially as described.

5. Asa new composition of matter, a solid or massive pyroxyline compound, of the variety employed for imitating natural substances, containing pyroxyline and di-nitro' toluol, substantially as set forth.

In testimony whereof I affix my signature, in presence of two witnesses, this 2d day of June 1890.

JOHN H. STEVENS.

Witnesses:

WM. II. BERRIGAN, J12, JAMES J. Coseaovn. 

